Organo-nickel salts as adhesion promotors for vulcanizable elastomers to metals

ABSTRACT

Adhesion of metals to vulcanizable elastomers is promoted by a process of incorporating into the elastomer and organo-nickel salt and then vulcanizing the elastomeric composition while it is in contact with the metal surface.

United States Patent [19] Cowell et a1.

1 Sept. 16, 1975 ORGANO-NICKEL SALTS AS ADHESION PROMOTORS FOR VULCANIZABLE ELASTOMERS TO IVIETALS Inventors: George K. Cowell, Brunswick, Ohio; David J, Cherry, Somers; William J. Considine, Pearl River, both of NY.

Assignee: Ciba-Geigy Corporation, Ardsley,

Filed: Oct. 10, 1973 Appl. No.: 404,971

References Cited UNITED STATES PATENTS 2.643173 6/1953 Wilkins .1 117/1287 2,912,355 11/1959 Formanek et a1 156/110 A 3,189,630 6/1965 Smutny 260/4575 R 3,310,575 3/1967 Spivack.. 260/4575 R 3,488,368 l/197O Spivack 260/4575 R 3,497,464 2/1970 Monroe et al. 156/327 3,723,489 3/1973 Dexter et a1 260/4585 S FOREIGN PATENTS OR APPLICATIONS 943,081 11/ 1963 United Kingdom 260/4575 N 2,251,318 4/1973 Germany 156/327 Primary Examiner-Ronald W. Griffin Attorney, Agent, or FirmChar1es W. Vanecek ABSTRACT Adhesion of metals to vulcanizable elastomers is promoted by a process of incorporating into the elastomer and organo-nickel salt and then vulcanizing the elastomeric composition while it is in contact with the metal surface.

8 Claims, No Drawings ORGANO-NICKEL SALTS AS ADHESION PROMOTORS FOR VULCANIZABLE ELASTOMERS TO METALS DETAILED DESCRIPTION- This invention relates to the bonding of vulcanizable elastomeric compositions to metals,

In the production of rubber articles, such as, for example, pneumatic tires, belts, conveyer belts provided with reinforcing metallic elements, tubes provided with reinforcing cords or wires, and, in general, in the production of all rubber articles in which rubber is reinforced with metal, it is necessary to obtain between the metal and the elastomeric composition a strong and durable bond in order to ensure a good efficiency and a long life for the articles produced.

It has now been unexpectedly found that unusually good bonds are produced between vulcanizable elastomeric compositions and metals when there is added to the vulcanizable elastomeric composition a compound of the generic formula (Organic Ligand) Nickel( Anion) I (lower )alkyl HO R wherein R is an alkyl, cycloalkyl or aryl hydrocarbon group of l2 or less carbon atoms, 1 has a value of from to 6, and has a value from I to 4, or

wherein 1 has a value of from 0 to 6, y has a value of from 0 to 4 and n has a value of from 0 to l, or

c u c o wherein R and R are independently of one another alkyl groups having from O to 6 carbon atoms and y has a value of from O to 4, or

4, (RCO D wherein R is an organic anion derived from carboxylic acids containing from l to 30 carbon atoms, preferably 2 to 18 carbon atoms, e.g., acetoxy, lauroyloxy, stearoyloxy, benzoyloxy, malonoyloxy, succinoyloxy, and the like; phenoxy including alkylphenoxy; alkyl and arylsulfates and -sulfonates; or

5. (RS(CH2J,,CO2-)- E wherein R is alkyl, monoalkylaryl or polyalkyl aryl containing from 4 to 24 carbon atoms, alkyl with a thioether linkage or a group of the formula wherein Z is oxygen, sulfur or the direct bond and n has a value of l or 2, or

wherein R and R independently of one another are hydrogen, alkyl, aryl, or the substituents N(R) (R) form part of a heterocyclic ring.

The compounds of formula I above containing the organic ligand described by formula A are prepared according to procedures described in US. Pat. No. 3,488,368.

The nickel is present in a free valence state or may be present in a metal complex in which part but not all of the free valence state of the: metal is satisfied by one or more organic or inorganic anions. Illustrative of such organic anions are the acyloxy group derived from carboxylic acids containing from I to 30 carbon atoms, preferably 2 to 18 carbon atoms, e.g., acetoxy, lauroyloxy, stearoyloxy, benzoyloxy, malonoyloxy, succinoyloxy, and the like; phenoxy including alkylphenoxy; ,alkyland arylsulfates and sulfonates; alkyland arylphosphates and -phosphonates and the like. Suitable inorganic anions include chlorides, bromides, iodide, fluoride, nitrate, cyanide, cyanate, thiocyanate, sulfate and the like. 1

The phenylalkyl group of the phosphinic acid moiety is substituted in the aromatic ring by a hydroxy group and one (z=) or two (z=l to 6) (lower)alkyl groups. These substituents may be located on the phenylalkyl group in a number of ways. It is generally desirable to utilize a 3,5-dialkyl-4-hydroxyphenylalkyl arrangement, e.g., 3,S-di-t-butyl-4-hydroxybenzylphosphinate. However, other arrangements such as 2-hydroxy-5- (lower)alkylphenylalkyl are also within the scope of the present invention.

The alkylhydroxyphenyl group is linked to the phosphinic acid group through a straight or branched chained alkylene group of from I to 4 carbon atoms, the number of carbon atoms being shown by the designation 1.

In addition to the alkylhydroxyphenylalkyl group, the phosphorus atom of the phosphinic acid group bears a hydrocarbon group of from 1 to 12 carbon atoms. This hydrocarbon group may be an aliphatic hydrocarbon group, notably alkyl and preferably (lower) alkyl, a cycloalkyl group, such as cyclopentyl, or cyclohexyl, or an aryl group such as phenyl, naphthyl, xylyl, and the like.

By the term alkyl when used in this specification is intended a branched or straight chained saturated hydrocarbon group having from 1 to l2 carbon atoms. When qualified by the term lower, the hydrocarbon chain will contain from about 1 to about 6 carbon atoms. Typical of such alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, isopentyl, hexyl, octyl, t-octyl, decyl, dodecyl, and the like.

A particularly useful subclass of the present invention are those compounds of the formula (lowcr)alkyl cording to procedures described in US. Pat. No.

The available valence bonds of the metal will be satisfled by one or more phosphonate or O-alkyl phospho- 5 nate groups and, if needed, by anions, organic or inorganic. The anion may be organic or inorganic. Illustrative of such organic anions are carboxylate, such as those derived from carboxylic acids containing from 1 to 30 carbon atoms, preferably 2 to 18 carbon atoms, e. g., acetate, laurate, stearate, benzoate, malonate, maleate, sficcinate, and the like; phenates and alkyl substituted phenates; alkyland aryl-sulfates and -sulfonates; alkyland aryl-phosphates and -phosphonates; and inorganic anions such as chloride, bromide, iodide, fluoride, nitrate, cyanide, cyanate,'thiocyanate, sulfate, and the like. I

The term alkyl is intended a branched or straight chained saturated hydrocarbon group having from 1 to about 30 carbon atoms. When qualified by the term lower," the hydrocarbon chain will contain from 1 to about 6 carbon atoms. Typical of such alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, isopentyl, hexyl, octyl, t-octyl, decyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, triacontyl and the like.

The phenyl group of phosphonate moiety is substituted by a hydroxy group and one (z=0) or two (z=l to 6) (lower)alkyl groups. These substituents may be located on the phenyl group in a number of ways. It is desirable to utilize a 3,5-dialkyl-4-hydroxyphenyl ar rangement, e.g., 3,5-di-t-butyl-4-hydroxybenzylphosphonate. However, other arrangements such as 2- hydroxy-4-(lower)alkylphenyl are also within the scope of the present invention.

The following formulae, in which R represents the group lowcrlnlkyl are typical structures of the compounds of this inven- Illustrative of the compounds usable in the present invention are the following compounds of formula I having organic ligand B:

nickel bis(o-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel 3,S-di-t-butyl-4-hydroxybenzylphosphonate nickel bis(o-octadecyl 3,5-di-t-butyl-4-hydroxybenzylphoshponate) nickel( 3 ,5-di-t-butyl-4-hydroxybenzylphosphonate- )acetate nickel-( o-n-butyl-3 ,5 -di-t-butyl-4-hydroxybenzylphosphonate )-chloride di-nickel-bis-(o-n-butyl'3,5-di-t-butyl-4- hydroxybenzylphosphonate)sulfate.

The compounds of Formula 1 above containing the organic ligand described by formula C are prepared according to procedures described in U.S. Pat. No. 3,189,630 for the nickel benzoates and analogously to procedures described in US. Pat. No. 3,723,489 for the nickel phenylalkanoate compounds.

Illustrative of the compounds usable in the present invention are the following compounds of formula I having organic ligand C:

nickel bis( 3,5-di-tertbutyl-4-hydroxybenzoate) nickel bis{3-( 3 ,5-di-tertbutyl-4-hydroxyphenyl) propionate}.

The compounds of formula 1 above containing the organic ligand described by formula D are known commercially available compounds. Illustrative of the compounds usable in the present invention are the following compounds of formula I having organic ligand D:

nickel acetate nickel benzoate nickel caprylate nickel citrate nickel cyclohexanebutyrate nickel 2-ethylhexoate nickel naphthenate nickel neodecanate e nickel octoate nickel oleate nickel propionate nickel stcarate nickel toluate.

The compounds of formula I above containing the organic ligand described by formula E are prepared according to procedures described in Belgium Pat. No. 754,891.

Illustrative of the compounds usable in the present invention are the following compounds of formula I having organic ligand E:

nickel n-octylthioacetate nickel n-hexadecylthioacetate nickel n-octadecylthioacetate nickel p-tert-butylphenylthioacetate nickel nbutylthiopropionate nickel n-dodecylthiopropionate nickel tert-dodecylthiopropionate nickel p-tert-butylphenylthiopropionate.

The compounds of formula I above containing the organic ligand described by formula F are prepared according to procedures described in British Pat. No. 943.081.

Illustrative of the compounds usable in the present invention are the following compounds of formula I having organic ligand F:

is provided a method of bonding a vulcanizable elasto meric composition to a metal surface during vulcanization which comprises adding to a vulcanizable elastomeric composition a compound of formula I in an amount of from 0.05 phr to 10 phr by weight based on the weight of the elastomer, and preferably from 0.1 to 5.0 phr, and vulcanizing the composition while it is in contact with the metal surface to provide a strong and durable bond. According to the present invention, there is also provided a composition which comprises an unsaturated vulcanizable elastomer, a vulcanizing agent, and a compound of formula I in an amount of from 0.05 phr to 10 phr by weight based on the weight of the elastomer, and preferably from 0.10 to 5.0 phr.

The unsaturated vulcanizable elastomeric composition may be produced by mixing the ingredients of the composition in the normal manner in an internal mixer, for example, a Banbury mixer, an extruder and/or on a two-roll mill. After mixing, the composition may be applied to a metal surface and vulcanized. After application to the metal surface, the composition is normally vulcanized at a temperature of from C to C. The time of vulcanization may be varied according to the vulcanization temperature and the properties desired in the vulcanizate, as is known in the art. Generally, as the vulcanization time: is increased, the bond strength increases. There is further provided a product of the method described in this paragraph.

The compounds of formula I can be used with any vulcanizable elastomer. All natural and/or synthetic rubbers are usable in the present invention. Such elastomers include polydienes such as polybutadiene or polyisoprene, including natural rubber; copolymers of dienes such as butadiene or isoprene with other copolymerizable monomers such as styrene, alphamethylstyrene, an acrylic ester, methylisopropenylke tone, isobutylene, acrylonitrile or an unsaturated carboxylic acid; halogenated rubbers such as polychloroprene or fluororubbers; interpolymers of one or more monolefins with a monomer which confers unsaturation on the interpolymer for example an unsaturated ethylene/propylene interpolymer such as an ethylene/- propylene/dicyclopentadiene terpolymer; sulphur-vulcanizable polyurethane rubbers; butyl rubber containing at least 0.8% unsaturation; and combinations of the above elastomers, e.g., natural rubber/butadienestyrene copolymer blends, a mixture of a saturated copolymer of ethylene and propylene with an unsaturated interpolymer of ethylene, propylene and a monomer comprising unsaturation in the interpolymer. etc.

In addition to the compounds defined by formula I, the compositions of this invention may contain other conventional additives including accelerators, activators, anti-cracking agents, antioxidants, antiozonants, anti-scorching agents, antistatic agents, dispersing agents, extenders, fillers, internal lubricants, plastic softeners, processing aids, retardars, tackifiers, vulcanizing agents, pigments, etc. These conventional ingredients and additives are added to the elastomeric material in suitable amounts in known manners to produce a vulcanizable composition based on the selected elastomer.

The vulcanizable compositions which may be bonded by the method of the present invention will preferably contain carbon black. The amount of carbon black included will depend upon the desired nature of the product. Since, although the hardness is increased by increased amounts of carbon black, the resilience of the rubber, when vulcanized, is reduced. Preferably, however, the amount of carbon black in the rubber is from 25 to 80 parts by weight of carbon black per 100 parts by weight of the elastomer in the compositions.

The use of sulphur as vulcanizing agents is preferred, since this ingredient is known to be capable of facilitating the bonding between the elastomeric composition and metals, and in particular, brass or zinc slated metals. The amount of sulphur in the synthetic rubber composition may be from 0.1 to 25 parts by weight, preferably from 0.5 to parts by weight, per 100 parts by weight of the vulcanizable elastomer.

Examples of accelerators useful in the invention are mercaptobenzothiazole or N-cyclohexylbenzothiazole- 2-sulpheneamide which may be present in an amount of, for example, from 0.1 to 6.0 parts by weight per 100 parts by weight of the elastomer.

The metals to which the elastomeric composition is to be bonded include iron, steel, cobalt, nickel, copper, zinc, titanium, vanadium, chromium, tin and mixtures of the above, more specifically brass and bronze. The preferred metals of this invention are steel or brass, bronze or zinc plated metals. [t is not necessary for the surface of the metal to be roughened before the com position is applied since the bond between the composition and the metal is not a mechanical one. However, it is preferred to free the metal surface of grease and dirt before the composition is applied.

The following examples, presented for illustration and not limitation, will further serve to typify the nature of the present invention.

EXAMPLE 1 Bonding of Natural Rubber to Brass Plated Steel Wire a. Preparation of Natural Rubber Stock One hundred parts of natural rubber (SMRSL) were placed in a size B Banbury Mixer preheated to about 1 10F and having a rotor speed of 1 16 rpm. After 0.5 minutes of mixing, 1.00 part stearic acid plus 5.00 parts of tackifier (Piccovar 420) were added. After mixing for an additional minute, 50.00 parts of carbon black Continex FEF (N550)) were added in two equal portions were added after 1.5 and 2.5 minutes of total mix- 5 ing time, respectively. Zinc oxide, 1.00 part was added after 3.5 minutes of total mixing time and the mix was swept down after 4.5 minutes of total mixing time. After mixing for an additional 1.5 minutes to make a total of 6 minutes, the entire mix was dumped at a temlO perature of about 320F.

b. Sample Preparation The stock obtained after Banbury mixing was cut into smaller samples, ranging in size from 50 to 100 grams which were subsequently milled on a two-roll mill at l5 [60F for 7 minutes, during which time 2.00 parts of sulfur, 0.75 parts accelerator (SANTOCURE NS) and either 1.60 or 1.00 parts of the organo-nickel salt were added. After 7 minutes of milling, the stock was sheeted.

The sheeted stock was cut into 0.5 X 8.0 inch strips and stacked to form two strips each weighing approximately 16 grams. The strips were freshened (lightly washed) with n-hexane prior to being placed in a curing mold.

The mold was preheated in a hydraulic compression press maintained at 290F for a minimum of 3 minutes. The mold was removed from the press, and loaded according to the following sequence: brass support plate (8 X 0.5 X 0.062 inch), rubber strip, brass plated steel wire sample, rubber strip, brass support plate and top plate of mold. The sample was cured for 23 minutes at 290F under a ram force of 23,000 pounds. After the 23 minute curing time, the mold was removed from the press and the rubber sample containing both the support plates and wire was removed from the mold and allowed to cool to ambient temperature (72F).

A description of the above sample preparation procedure is found in ASTM Test D2229-68.

0. Testing Method After standing at ambient temperature for 18 to 24 hours, the wires were pulled from the rubber stock using an lnstron Testing machine, in accordance with the testing procedure set forth in ASTM test 2229-68, but with the modifications described in A. E. Hicks, et

al. in Rubber Chemistry and Technology, 45, 2648 d. Test Results Listed in Table l are the test results obtained according to the procedure outlined above.

TABLEI -Continued Rubber Additive Pull-Out Adhesion Organic Ligand Stock No. Concentration Force Factor 0 H ,C y-O- 5 1.6 27 1.3

HO -CH CH C-O 2 1.6 29 1.4

H C SCH LIO- 5 1.6 1.2

H C SCH Ch y 5 1.6 l 28 1.3

Blank 4 22 1.0

Blank 2 20 1.0

Blank 5 21 1.0

Pull-Out Force For Additive Compound Pull-Out Force for Blank EXAMPLE 2 Adhesion of Styrene-Butadiene Copolymer to Brass Plated Steel Wire Preparation of Styrene-Butadiene Copolymer Adhesion Factor minutes, then swept down and the mixing continued for 2 more minutes for a total mixing time of 6 minutes, at which time the entire mix was dumped at a temperature of about 345F.

b. Sample Preparation The stock obtained after Banbury mixing was cut into smaller samples, ranging in size from 50 to 100 grams. These were subsequently milled on a two roll mill at 180F for 7 minutes during which time 1.24 parts of sulfur, 0.64 parts of Santocure NS, 0.14 parts of tet ramethylthiuram monosulfide and 1.00 parts of nickel bis(o-n-butyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate) were added. After 7 minutes of milling, the stock was sheeted.

The sheeted stock was cut into 0.5 X 8.0 inch strips and stacked to form two strips each weighing approximately 16 grams. The strips were freshened (lightly washed) with n-hexane prior to being placed in the curing mold.

The mold was preheated in a hydraulic compression press maintained at 300F for a minimum of 3 minutes. The mold was removed from the press and loaded according to the following sequence: brass support plate (8 X 0.5 X 0.062 inch), rubber strip, brass plated steel wire samples, rubber strip, brass support plate and top plate of mold. The sample was cured for 24 minutes at 300F under a ram force of 23,000 pounds. After the 24 minutes curing time, the mold was removed from the press and the rubber sample containing both the support plate and wires were removed from the mold and allowed to cool to ambient temperature (72F).

c. Test Method After standing at ambient temperatures for 18 to 24 hours, the wires were pulled from the rubber stock using an lnstron Testing machine according to ASTM Test 2229-68 but including the modifications described by A. E. Hicks, et al. in Rubber Chemistry and Technology, 45, 26-48 (1972).

(1. Test Results The average force required to pull the wire from 0.5 inches of rubber was 60 pounds while the average force required to pull the wire from a formulation containing all of the ingredients except the additive compound was 17 pounds.

EXAMPLE 3 Adhesion of Ethylene-Propylene Terpolymer (EPDM) Rubber to Brass Plated Steel Wire a. Preparation of EPDM Rubber Stock The EPDM Rubber Stock was prepared by placing 100.00 parts of EPDM rubber (EPSYN 40A from C0- polymer) in a size B Banbury Mixer preheated to about F and having a rotor speed of l 16 rpm. After mixing for 0.5 minutes, 1.00 parts of stearic acid were added and mixed for another 0.5 minutes. One-half of 150.00 parts of carbon black FEF (N650) was then added and mixed for an additional 0.5 minutes. Then the remaining one-half of the carbon black, 5.00 parts of zinc oxide and 100.00 parts of process oil (Flexon 580) were added, the stock was mixed for another 4.5 minutes and then dumped. The total mixing time was 6 minutes and the dump temperature was about 335F.

b. Sample Preparation The Banbury mixed stock was cut intosmaller samples, ranging in size from 50 to 100 grams. These were milled on a two roll mill at 180F for 7 minutes during which time 1.50 parts of sulfur, 1.50 parts of tetramethylthiuram monosulfide, 0.50 parts mercaptobenzothiazole and 1.60 parts of nickel bis(o-ethyl-3.5-di-tbutyl-4-hydroxybenzylphosphonate) were added. After 7 minutes of milling, the stock was sheeted.

The sheeted stock was cut into 0.5 X 8.0 inch strips and stacked to form two strips each weighing about 16 grams. The strips were freshened (lightly washed) with n-hexane prior to being placed in the curing mold.

The mold was preheated in a hydraulic compression press maintained at 300F for a minimum of 3 minutes. The mold was removed from the press and loaded according to the following sequence: brass support plate (8 X 0.5 X 0.062 inch), rubber strip, brass plated steel wire samples, rubber strip, brass support plate and top plate of mold. The sample was cured for 32 minutes at 300F under a ram force of 23,000 pounds. After the 32 minutes curing time, the mold was removed from the press and the rubber sample containing both the support plates and wires was removed from the mold and allowed to cool to ambient temperature (72F).

c. Test Method After standing at ambient temperature for 18 to 24 hours, the wires were pulled from the rubber stock using an lnstron Testing machine according to Test 2229-68, but including the modifcations described by A. E. Hicks et al. in Rubber Chemistry and Technology, 45, 26-48 (1972). :4 i

d. Test Results i The average force required to pull the wire from 0.5 inches of rubber was 34 pounds while the average force to pull the wire from a formulation containing all of the ingredients except the additive compound was 3 canizable elastomeric composition and a metal surface to provide a strong and durable bond, which method consists essentially of I a. adding to a vulcanizable elastomeric composition from 0.05 phr to phr by weight based on the weight of the elastomer of a compound of the generic formula I 7 (Organic Ligand) Nickel(Anion) I wherein the organic ligand is represented by one of the following generic formulas and the anion is represented by one of the following generic formulas or is an inorganic anion:

wherein R is an alkyl, cycloalkyl or aryl hydrocarbon group of 12 or less carbon atoms, z has a value of from 0 to 6, and has a value from 1 to 4, or

wherein 2 has a value of from 0 to 6, y has a value of from to 4 and n has a value of from 0 to l, or

wherein Z is oxygen, sulfur or the direct bond and n has a value of l or 2, or

Ni O o wherein R and R independently of one another are hydrogen, alkyl, aryl, or the substituents N(R) (R) form part of a heterocyclic ring, and

b. vulcanizing the composition while it is in contact with the metal surface.

8. The method of claim 6 wherein the vulcanizable elastomer is natural rubber or ethylene-propylene terpolymer and the compound of formula I has the for 2. The method of claim 1 wherein the vulcanizable elastomer is selected from natural rubber, styrenebutadiene copolymer, or ethylene-propylene terpolymer.

3. The method of claim 1 wherein the compound of formula I is present in an amount of from-0.1 to 5.0 phr by weight, based on the weight of the elastomer.

4. The method of claim 1 wherein the elastomeric composition contains carbon black.

5. The method of claim 1 wherein the vulcanizing agent is sulfur. 

1. A METHOD OF IMPROVING ADHESION BETWEEN A VULCANIZABLE ELASTOMERIC COMPOSITION AND A METAL SURFACE TO PROVIDE A STRONG AND DURABLE BOND, WHICH METHOD CONSISTS ESSENTIALLY OF A. ADDING TO A VULCANIZABLE ELASTOMERIC COMPOSITION FROM 0.05 PHR TO 10 PHR BY WEIGHT BASED ON THE WEIGHT OF THE ELASTOMER OF A COMPOUND OF THE GENERIC FORMULA (ORGANIC LIGAND) NICKEL(ANION) WHEREIN THE ORGANIC LIGAND IS REPRESENTED BY ONE OF THE FOLLOWING GENERIC FORMULAS AND THE ANION IS REPRESENTED BY ONE OF THE FOLLOWING GENERIC FORMULAS OR IS AN INORGANIC ANION:
 2. The method of claim 1 wherein the vulcanizable elastomer is selected from natural rubber, styrene-butadiene copolymer, or ethylene-propylene terpolymer.
 3. The method of claim 1 wherein the compound of formula I is present in an amount of from 0.1 to 5.0 phr by weight, based on the weight of the elastomer.
 4. The method of claim 1 wherein the elastomeric composition contains carbon black.
 5. The method of claim 1 wherein the vulcanizing agent is sulfur.
 6. The method of claim 1 wherein the vulcanizable elastomer is natural rubber, styrene-butadiene copolymer, or ethylene-propylene terpolymer and the compound of formula I has the organic ligand and anion both represented by formula B.
 7. The method of claim 6 wherein the vulcanizable elastomer is natural rubber or styrene-butadiene copolymer and the compound of formula I has the formula
 8. The method of claim 6 wherein the vulcanizable elastomer is natural rubber or ethylene-propylene terpolymer and the compound of formula I has the formula 